Production of nitrogenous vat dyestuffs of the azine series and the products



Patented Nov. 22, 1932 UNITEDJSTATESPATENT; FF CE MAX ALBERT xunz, or MN-NHEIM, AND

ANILINEWORKS,INC., 01'' HEN] YORK,

KAR-nKoEBnRLE, or LunwIcsnArnN-oN-THE- RHINE, GERMANY, ASSIGNQRS 'roenNERAn N. Y., A CORPORATION OF DELAWARE PRODUCTION or nrrrRoGENoUs vA'rnYEs'rUFrsor with AziNnsEmnsANn THE 7 rnonucrs n.

No Drawing. Application filledtictober 22,1928 Serial.1 T o. 314,3 1 1,and in Gerina ny November 3, 19 27.f v I The present invention relatesto the pro duction of nitrogenous vat dyestufis contain-: ing adibenzanthrone or iso-d1benZanthroneradicle.

We have found that valuable vat dyestufi 's' are obtained by condensingdibenzanthrone or iso-dibenzanthron'e, or a derivative thereof Which arehereinafter referred to for the sake of brevity as dibenzanthrones,containing at least one nitrogen atomvto which a reactive hydrogen atomis attached With an oxygen free six memberedringCOhlPOliIlClCOIltfilIllIlg at least one nitrogen atom in the nucleus andsubstituted by at least one halogenatom, such as halogenpyridine,halogenpyrimidine 24 dichlor- 6 methylpyrimidine, 2.4.6-trichlor-ipyrimidine, cyamiric chlorid, "2 methyl-4e6- dichloro-1.3.5-triazine,2-phenyl-4.6j-dichloro-1.3.5-triazine, 2.4-diphenylf6-chloro-1.3.5triazine and thelike. t r v The condensation is'suitably carriedout insolvents or diluting mediaof ahi'ghboiling point, such as for instancenitroben zene, ni

tronaphthalene,trichlorobenzene andit helike, preferably in the presenceof acidffixing agents, such as sodium acetate, andcondens ingcata1ysts,'for1 instancemeta-l or metal compounds, such ascopper,'copperoxide, copper carbonate, mercury oxide, aluminiumand thelike.' I When condensing one of theaforesaidheterocyclic compoundscontaining several halo gen atoms, the Whole or onlya portion of thehalogen atoms may be replaced, as desired,

by the nitrogenous dibenzanthronyl or Tisodibenzanthronyl radicle. Thereactive halogen atoms remainingin the latter case in the condensationproduct maybe further brought to reaction With suitable substances, suchas aminoanthraquinones and their derivatives, or other, amines, inparticular aromatic amines, or compounds containingpO I-I- or SH-groupsfor instance alcohols, phenols,

thiophenols' of the aliphatic or' aromatic series. l, The said lattercompounds may also be condensed With thefsaid heterocycliccompoundssimultaneously with; the aminodibens zanthrones or before. Particularlyvaluable dyestuffs obtainable injthe" aforedescribed manner are thosederived from the haloge- C general formula Y-N-R in Which? stands for adibenzanthrone.

radicie, X for further substituents and Yfor hydrogen or an alkylgroiip. V

The new vat dyestuii's obtainable accordingto the present invention are,for the most:

part, produced With an excellent yield. F or. the purposeuofpurification, they may be, treated in the form of pastes with oxidizing.

agents, for instance hypochlorite, or'recrysing point-{but in manyinstances, ,a simple boiling with solvents is sufficient. Accord-X ingto the selection of the acting components;

vat dyestuilsrof ivery varied character are",

obtained which give extremely fast dyeings, in a'great variety of,shades, on vegetablev fibres from the vat.

The following examples Will illusf trate the nature of the saidinvention which however is not limited thereto. The parts are by Weight;

- Example 1 v A suspension of 470 partsoflthe "aminodibenzanthroneobtainable by reducing 1 the nitrodibenzanthrone obtained according tolUS. Patent $10,796,393, in 3000 parts. of 7 parts of cyanuric chlorid, 50 parts of sodiumacetate and 6 arts of co ercarbonate un-;

til the precipitated dyestuft' is'free from halogen, or still containsonly small amounts of halogen. When'cold, the product is'filtered .bysuctionand is treated in the usualmanner;

nitrobenzene, is boiled and stirredvvith blue dyeings on cotton from'ablue alkaline.

hydrosulfite Vat. A

By condensing 470 parts of the same aminodibenzanthrone I 122 parts ofjcya heated at about 200 usual manner.

4- .3 acetate,

4n solves to a giving green .blue dyeings on the vegetable iibre from 'ablue'vat. I

' Ewav rvple 2 470 parts of aininodibenzanthrone, 190

parts of cyanuricchlorid are stirred and (l, for half an hour, in 1000parts of-nitrobenzene, whereupon aat'urther 1000 parts of nitrobenZene,250 parts of sodium acetate,120 parts of copper carbonate and 450 partsor" l-aminoanthraquinone, are

15 added. Stirring is continued, at the boiling point of-nitrobenzene,until a sample of the reactio'nproduct is found to be free, or nearlyso, from halogen. i WVhen cold, the product is filtered by suction andis treated in the The dyestufl, which is obtained in the form of agreenish black powder, dissolves to a-wine red solution in concentratedsulfuric acid, and gives very fast yellowgreen dyeings on cotton from avio- Example 3 94 parts of aminodibenzanthrone, 18.5

parts of cyanur-ic chlorid,20 parts of sodium of 1.4aminomethoxyanthraquinone obtains I able by reducing thenitrodibenzanthrone prepared according to the U. S. Patent No.796,393,.are stirred and-boiled in 2000 parts of nitrobenzene, until theformation :of the dyestuflzis completed. WVhen cold, the product isfiltered by suction, and treated as usual. 7 The dyestuiflof which anexcellent yield is obtained in the form of a black powder,disvtratedsulfu 'ic acid, and gives extremely fast-, blue black dyeingson cotton from a blue, alkaline hydrosulfite vat.

' Example 4 v I A suspension of 47 parts of monoaminoiso-dibenzanthrone(prepared by. reducing the V inon'onitro -'iso'-dibenz anthroneobtainable by the action of nitric'ac-id on iso-dibenzanthrone innitrobenzene) in 1500 parts of nitrobenzene, is mixed with the additionof 20 partsof sodium acetate and 7 parts of copperoxid at a temperatureofbetween 80 and 100C. with a solution warmed to between and C. of 18.5.parts of 2.4t.6-trichlor 1;3.5-triazine in 600 parts of nitrobenzene andthemixture heated for 2 hours at C. and for A 'hours at 195. to 200? 0-.while stirring.

A 60 After cooling the reaction product is filtered by suction. Thedyestufi, a bluepowder, dissolvesin concentrated sulfuric acid to agreen 7 solution and dyes cotton dark blue shades of excellent fastnessfrom a blue vat;

5165- The crude-dyestuit maybe purified, if

"atom is attached.

1 part of cupric oxid and 25 parts bluish red solution in concen-vdesired, by treating its aqueous paste with I hypochlorite orotheroxidizing agents.

What we claim is 1. A process 'of producing new' evat; dyestufis whichcomprises condensing oxygen' free six'membered ring compound containing'at least one nitrogen atom in the nucleus and substituted by at leastone halo 7 gen atom with a. dibenzanthrone containing a nitrogen atom towhich a reactive hydrogen 2. A processof producing stuffs whichcomprises con e taining at least one nitrogen atom in the nucleusandsub'stituted by at least'one lialopoint.

gen-free six memberedring-compound containing. at leasthone nitrogen'atom in the agent.

, process of producing'new vat,dye stuliswh ch comprises condensing anfoxy process of producing new "vat "dyenew vat dye.- L nsingan oxygenfree six membered ring compound 0on gen atom with a dibenz'anthro'necontaining a nitrogen atom to which a reactive hydrogen atom 1S attachedin a diluent of ahigh boiling stuffs which comprises condensing anoxy'-- gen-free six membered ring compound icon-1' taming at leastionenitrogen atom in the nucleus and substituted by at least one, halo"- genatom witha dibenzanthrone containing a nitrogen atom to whichreactivejhydrogen atom is attached in a diluent of'a highboil ing pointinthe presence of an acid-fixing agentand a condensing catalyst. j

w 5. A process of producing new vat dyes'tulis which comprisescondensing a.' 1.3.;5-

triazine substituted b'y 'at least one halogeiif atom with'dibenzanthrone containing a nitrogen atom to which a reactive hydrogenatom is attached.

6. A process of producingnew vatfdyestuiis which comprises condensingcyanurie chlorid with a dibe'nzanthrone containing a nitrogen atomtowhich'a' reactive hydrogen 1 atom is'attache'd. I I

7. A process of producing new vat dyestuffs' which comprises condensingcyanuri'c chlori'd with adibenzanthrone containing a nitrogen atom towhich a reactive hydrogen atomis attached and an aromatic compoundcontaining a NHg-',"NH-, O H- or SH-group.

8. A proce'ssfof producing new vat dye stuffs which comprises condensingan oxygen-free six membered ring compound containi'n-g' at least onenitrogen atom in the nucleus and substituted by" three halogen f atomswith a diben'zantlirone containing a nitregenatom to which a. reactive"hydrogen I atom is attached and an aromatic compound gen, an alkyl, anaryl, or

'i in which R stands containinga NH NH-, OH- or SH-group. 9. process ofproducing new vat dyestuffs which comprises condensing cyanuric chloridwith a dibenzanthrone containing. a nitrogen atom to which a reactivehydrogen atom is attached and an aromatic amine.

10. A process of chlorid witha dibenzanthrone containing a nitrogen atomto which a reactive hydrogen atom is attached and an aminoanthraqulnone.

11. As new articlesof manufacture vat dyestuffs of the general formula iif in which R stands for a dibenzanthrone radicle, 'Y for hydrogen or analkyl group and X for hydrogen, halogen, an alkyl, an n Q aryl or anarylimino group. 12. As new articles of dyestuffs of the general formulaat ax \Z/ X45 ax in which R stands for a dibenzanthrone radicle, Y forhydrogen or an alkylgroup and one X for hydrogen, halogen, an alkyl, anaryl, or an arylimino group andthe other X for an arylimino group.' 7

14. Vat dyestuffs of the general formula for a dibenzanthrone radicle, Yfor hydrogen or an alkyl group and one X for hydrogen, halogen,

an aryl, or an arylimino group and the other for an aminoanthraquinonegroup. j 15. The vat dyestufl forming a blackproducing new vat dyestuffswhich comprises condensing cyanuric V manufacture vat in which eachpowder, dissolving toa bluish-red solution in concentrated sulfuricacid, giving extreme- I on cotton from a ly fast, blue black dyeings tothe formula blue vat and corresponding i Y N ILA i-XI 1'. N t stands fordibenzanthrone an anthraquinone radicle and in. which R radicles, R forg Y for hydrogen or an alkyl group. 7

16. The vat dyestufl forming a green black powder, dissolving to a winered solution in concentrated sulphuric acid, giving very fast yellowgreen dyeings on cotton from a violet vat and corresponding to theformula nan-R radicle.

R stands for a dibenzanthrone 17. The vat dyestuff, forming a blackpowder, dissolving to a bluish red solution in concentrated sulphuricacid, giving extremely fast blue black dyeings on cotton from a blue vatand corresponding to the formula V 4 rad cle.

in which each R stands fora dibenzanthrone' In testimony whereof wehavehereunto set our hands.

MAX ALZBERT KUNZL KARL KOEBERLE. 1

an alkyl,

